The catalytic potential of chloroperoxidase (CPO) immobilized on mesoporous materials was evaluated for the oxidation of 4,6-dimethyldibenzothiophene in water/acetonitrile mixtures. Two different types of materials were used for the immobilization: a metal containing Al-MCM-41 material with a pore size of 26 angstrom and SBA-16 materials with three different pore sizes: 40, 90 and 117 angstrom. The SBA-16 40 angstrom did not retain any CPO. The nature and the pore size of the material affected the catalytic activity of the enzyme as well as its stability. Compared to the free enzyme, the thermal stability of CPO at 45 angstrom was two and three times higher than when immobilized on Al-MCM-41 and SBA-16 90 angstrom, respectively.